Na-ion batteries are considered a promising next-generation battery alternative to Li-ion batteries,due to the abundant Na resources and low cost.Most efforts focus on developing new materials to enhance energy densit...Na-ion batteries are considered a promising next-generation battery alternative to Li-ion batteries,due to the abundant Na resources and low cost.Most efforts focus on developing new materials to enhance energy density and electrochemical performance to enable it comparable to Li-ion batteries,without considering thermal hazard of Na-ion batteries and comparison with Li-ion batteries.To address this issue,our work comprehensively compares commercial prismatic lithium iron phosphate(LFP) battery,lithium nickel cobalt manganese oxide(NCM523) battery and Na-ion battery of the same size from thermal hazard perspective using Accelerating Rate Calorimeter.The thermal hazard of the three cells is then qualitatively assessed from thermal stability,early warning and thermal runaway severity perspectives by integrating eight characteristic parameters.The Na-ion cell displays comparable thermal stability with LFP while LFP exhibits the lowest thermal runaway hazard and severity.However,the Na-ion cell displays the lowest safety venting temperature and the longest time interval between safety venting and thermal runaway,allowing the generated gas to be released as early as possible and detected in a timely manner,providing sufficient time for early warning.Finally,a database of thermal runaway characteristic temperature for Li-ion and Na-ion cells is collected and processed to delineate four thermal hazard levels for quantitative assessment.Overall,LFP cells exhibit the lowest thermal hazard,followed by the Na-ion cells and NCM523 cells.This work clarifies the thermal hazard discrepancy between the Na-ion cell and prevalent Li-ion cells,providing crucial guidance for development and application of Na-ion cell.展开更多
The unique oxygen stacking sequence of O2-type structures restricts the irreversible transition metal movement into Li vacancies for the delithiated Li-rich layered oxides(LLOs)and maintains outstanding voltage stabil...The unique oxygen stacking sequence of O2-type structures restricts the irreversible transition metal movement into Li vacancies for the delithiated Li-rich layered oxides(LLOs)and maintains outstanding voltage stability.However,the ion-exchange synthesis promotes the Mn-ion valence reduction and aggravates the Jahn-Teller(J-T)distortion alongside disproportionation.Since the main oxidation state of the Mn ions is+4 in the traditional O3-type LLOs,synergistic effects of the O2-type and O3-type structures are expected in the O2/O3 diphasic Li-rich material.Herein,O2/O3 biphasic intergrowth LLOs were rationally designed,and the synergic optimization of the biphasic structure was planned to retard the J-T effect.The O2/O3 intergrowth nature was confirmed,and the percentages of the O2 and O3 phases were 56%and 44%,respectively.Density functional theory calculations demonstrated that the Mn^(2+)(EC)sheath had a remarkably lower energy barrier than the Li^(+)(EC)sheath.This finding suggests that Mn^(2+)ions that are dissolved into the electrolyte accelerate the electrolyte oxidization,so the deposition of the cathode electrolyte interface for pristine O2-LLOs causes a high electrochemical impedance.The designed O2/O3 biphasic LLOs boost the capacity stability and suppress the voltage drop upon repeated Li^(+)de-intercalation.The phase regulation strategy offers great potential for developing low-cost LLOs with enhanced structural stability for advanced Li-ion batteries.展开更多
In optimizing fast charge capability,mitigating side reaction rate,and unveiling particle cracking tolerance for Li-ion batteries(LIBs),the galvanostatic charge–discharge(GCD)at different charge/discharge rates,the s...In optimizing fast charge capability,mitigating side reaction rate,and unveiling particle cracking tolerance for Li-ion batteries(LIBs),the galvanostatic charge–discharge(GCD)at different charge/discharge rates,the static electrochemical impedance spectroscopy(SEIS)under open circuit voltage(OCV)conditions,and the dynamic EIS(DEIS)under dynamic conditions are widely used to investigate charge transfer reactions in LIBs.In spite of great progresses achieved,it is still an open question how to decouple charge transfer reactions under dynamic conditions,especially under conditions of different charge/discharge rates and state of charges(SOCs).To address the above challenges,this work develops a unified framework to digitize,visualize,and finally decouple charge transfer reactions in LIBs under dynamic conditions.In detail:(i)a set of matrix-based numerical solutions to GCD,SEIS,and DEIS are deduced for LIBs;(ii)an open-source DEIS-Toolbox@LIB to digitize/visualize charge transfer reactions is developed;(iii)EIS under dynamic and OCV conditions are discriminated;and(iv)a dynamic decoupling of charge transfer reactions is achieved with respect to core parameters under dynamic conditions for LIBs.The developed framework serves to digitize/visualize/decouple charge transfer reactions under dynamic conditions,and then to unveil limiting factors of fast charge/discharge and triggering mechanisms of side reactions for batteries.展开更多
Developing cost-effective single-crystalline Ni-rich Co-poor cathodes operating at high-voltage is one of the most important ways to achieve higher energy Li-ion batteries. However, the Li/O loss and Li/Ni mixing unde...Developing cost-effective single-crystalline Ni-rich Co-poor cathodes operating at high-voltage is one of the most important ways to achieve higher energy Li-ion batteries. However, the Li/O loss and Li/Ni mixing under high-temperature lithiation result in electrochemical kinetic hysteresis and structural instability. Herein, we report a highly-ordered single-crystalline LiNi0.85Co0.05Mn0.10O2(NCM85) cathode by doping K+and F-ions. To be specific, the K-ion as a fluxing agent can remarkably decrease the solid-state lithiation temperature by ~30°C, leading to less Li/Ni mixing and oxygen vacancy. Meanwhile, the strong transitional metal(TM)-F bonds are helpful for enhancing de-/lithiation kinetics and limiting the lattice oxygen escape even at 4.5 V high-voltage. Their advantages synergistically endow the single-crystalline NCM85 cathode with a very high reversible capacity of 222.3 mAh g-1. A superior capacity retention of 91.3% is obtained after 500 times at 1 C in pouch-type full cells, and a prediction value of 75.3% is given after cycling for 5000 h. These findings are reckoned to expedite the exploitation and application of high-voltage single-crystalline Ni-rich cathodes for next-generation Li-ion batteries.展开更多
With the widespread adoption of electric vehicles and energy storage systems,predicting the remaining useful life(RUL)of lithium-ion batteries(LIBs)is critical for enhancing system reliability and enabling predictive ...With the widespread adoption of electric vehicles and energy storage systems,predicting the remaining useful life(RUL)of lithium-ion batteries(LIBs)is critical for enhancing system reliability and enabling predictive maintenance.Traditional RUL prediction methods often exhibit reduced accuracy during the nonlinear aging stages of batteries and struggle to accommodate complex degradation processes.This paper introduces a novel adaptive long short-term memory(LSTM)approach that dynamically adjusts observation and prediction horizons to optimize predictive performance across various aging stages.The proposed method employs principal component analysis(PCA)for dimensionality reduction on publicly available NASA and Mendeley battery datasets to extract health indicators(HIs)and applies K-means clustering to segment the battery lifecycle into three aging stages(run-in,linear aging,and nonlinear aging),providing aging-stage-based input features for the model.Experimental results show that,in the NASA dataset,the adaptive LSTM reduces the MAE and RMSE by 0.042 and 0.043,respectively,compared to the CNN,demonstrating its effectiveness in mitigating error accumulation during the nonlinear aging stage.However,in the Mendeley dataset,the average prediction accuracy of the adaptive LSTM is slightly lower than that of the CNN and Transformer.These findings indicate that defining aging-stage-based adaptive observation and prediction horizons for LSTM can effectively enhance its performance in predicting battery RUL across the entire lifecycle.展开更多
The integration of photocatalysis with electrochemical energy storage offers promising solutions for offgrid power supply. Herein, carbon cloth-supported TiO_(2)nanorod arrays are engineered as a model platform to exp...The integration of photocatalysis with electrochemical energy storage offers promising solutions for offgrid power supply. Herein, carbon cloth-supported TiO_(2)nanorod arrays are engineered as a model platform to explore photoelectrochemical synergy in integrated photo-rechargeable lithium-ion batteries(PRLiBs). Through operando characterizations and theory calculations, we found that photoexcitation lowers the Li^(+)migration barrier by 0.16 eV through electronic states redistribution near the Fermi level,thereby accelerating Li^(+)transport and enhancing the intercalation process during photo-assisted charging and discharging. Three key principles governing dual operational modes(light-assisted charge/discharge and pure light charging) are established for PRLiBs:(i) the capacity enhancement during photoassisted charging is primarily due to photocatalytic Li^(+)extraction via hole-driven oxidation at the TiO_(2)/electrolyte interface and electric double-layer reconstruction;(ii) the long-standing controversy in solar-to-electricity conversion efficiency(g) is resolved by introducing a polarization-decoupled model to quantify g, distinguishing genuine catalytic contributions from parasitic self-charging effects;and(iii)during light-only charging without external bias, the capacity increase is predominantly driven by the photocatalytic oxidation of the TiO_(2)photoelectrode, a single-electrode process without electron transfer through an external circuit, distinct from conventional dual-electrode charging. This work lays a solid theoretical foundation for understanding the mechanisms of PRLiBs and provides precise guidelines for g calculations, offering valuable insights for the future development of photo-energy storage devices.展开更多
Sulfide-based all-solid-state lithium metal batteries(ASSLMBs)have garnered significant attention due to their potential for high energy density and enhanced safety.However,their practical application is hindered by c...Sulfide-based all-solid-state lithium metal batteries(ASSLMBs)have garnered significant attention due to their potential for high energy density and enhanced safety.However,their practical application is hindered by challenges such as uneven lithium(Li)deposition and the growth of Li dendrites.In this contribution,we propose an amorphous fluorinated interphase(AFI),composed of amorphous LiF and lithiated graphite,to regulate the interfacial Li-ion transport kinetics through in-situ interface chemistry.Amorphous LiF,which exhibits a significantly enhanced Li-ion diffusion compared to its crystalline counterpart,works synergistically with lithiated graphite to promote both short-range and long-range Li-ion transport kinetics at the Li/electrolyte interface.As a result,the Li anode with AFI demonstrates a remarkably enhanced critical current density of 1.6 mA cm^(−2)and an extended cycle life exceeding 1100 h.The Li||LiNi_(0.6)Co_(0.2)Mn_(0.2)O_(2)full cell also achieves a high discharge capacity of 125.7 mA h g^(−1)and retains 71.2%of its initial capacity after 200 cycles.This work provides valuable insights into the rational design of artificial anodic interphase to regulate interfacial Li-ion transport kinetics in ASSLMBs.展开更多
Increasing the charging cut-off voltage can significantly enhance the energy density of LiCoO_(2).However,the continuous deterioration of interface structure and transport kinetics under high voltage poses challenges ...Increasing the charging cut-off voltage can significantly enhance the energy density of LiCoO_(2).However,the continuous deterioration of interface structure and transport kinetics under high voltage poses challenges to electrochemical stability.This work proposes to in-situ construct a uniform element gradient modification structure on the surface and subsurface of LiCoO_(2).The modification structure contains an Sb_(2)O_(3)&SbF_(x)composite coating layer and an Sb-F doped spinel-like transition layer,simultaneously.The modified sample maintains an initial discharge specific capacity of 221.2 mA h g^(-1)and a capacity retention of 86%after 200 cycles at 3–4.6 V and 0.5 C.Moreover,it has a discharge specific capacity of163.3 mA h g^(-1)at a high rate of 5 C.Meanwhile,combining highly electronegative Sb^(3+)&F^(-)that widen the Li^(+)transport channel with the amorphous coating of F^(-)doped Sb_(2)O_(3)with higher conductivity improves the interface transport kinetics.This breaks the stereotypical view in traditional concepts that fluorinated coatings or inert metal oxide coatings inhibit Li^(+)transport.Moreover,the inert composite coating combined with Sb–O–F with high bond energy stabilizes the surface structure.A series of characterizations confirm that the joint improvement of interface structure stability and transport kinetics significantly enhances the electrochemical performance of LiCoO_(2).展开更多
It is of great importance to explore sustainable and eco-friendly recycling strategies for spent Li-ion batteries(LIBs).As such,the closed-loop resynthesis of LiNi_(x)CoyMn_(z)O_(2)(NCM)becomes recently popular as exe...It is of great importance to explore sustainable and eco-friendly recycling strategies for spent Li-ion batteries(LIBs).As such,the closed-loop resynthesis of LiNi_(x)CoyMn_(z)O_(2)(NCM)becomes recently popular as exemplified by the commercialization of low-and mid-Ni content NCM(33%-60%).However,there has been suspicion as to the successful deployment of Ni-rich NCM resynthesis process.Therefore,we systematically increase the Ni content of NCM from 60%to 90%from the industrial leachate of spent LIBs containing various metallic and nonmetallic impurities.The utilization rate of the leachate decreases from 71.8 mol%for NCM622 to 18.0 mol%for NCM955 as the Ni content in the NCM composition increases with the Co recycling rate being 100%in all resynthesized NCM(RNCM).The physicochemical and electrochemical properties of RNCM are systematically compared with its pristine NCM counterparts.As a result,various physicochemical properties of RNCM including impurity content,crystallographic information,morphology,particle size,porosity,specific surface area,elemental distribution,residual lithium compounds,and thermal stability are correlated with its electrochemical properties.It is found out that Al is the most critical impurity that determines the physicochemical and electrochemical properties of RNCM.It is noteworthy that RNCM955 prepared from spent LIBs without any purification step surpasses NCM955 in terms of rate and cycle performance.Further,this resynthesis approach toward Nirich NCM could meet the forthcoming 2031 EU's legislative target on the mandatory minimum recycling usage of valuable metals from spent LIBs.The anode active material was resynthesized using industrial leachate as the maximum.The amount of leachate used and the amount of impurities were proportional.展开更多
Tailoring 1D nanotubes with refined interfacial interactions and optimized adsorption sites presents a highly promising yet challenging strategy for advancing Na/Li-ion batteries(SIBs/LIBs).Herein,the intertwined yard...Tailoring 1D nanotubes with refined interfacial interactions and optimized adsorption sites presents a highly promising yet challenging strategy for advancing Na/Li-ion batteries(SIBs/LIBs).Herein,the intertwined yardlong bean-like Fe_(9)Ni_(9)S_(16)/FeS heterostructures with sulfur vacancies encapsulated in N-doped carbon nanotubes(3 N-Fe_(9)Ni_(9)S_(16)/FeS-3@CNTs)are controllably synthesized through Fe/Ni-catalyzed pyrolysis of dicyandiamide followed by sulfidation strategies.1D nanotubes with robust outer walls and internal cavity structures shorten the diffusion paths of ions/electrons and buffer volume expansion and aggregation of active materials.The Fe_(9)Ni_(9)S_(16)/FeS heterostructure provides a powerful driving force for charge transfer by forming built-in electric fields,optimizing ion adsorption,while the Fe_(9)Ni_(9)S_(16)features a wider interlayer spacing that allows for frequent Na+/Li+insertion and extraction,thereby enhancing the reaction kinetics within the electrode.Driven by these synergistic factors,the 3 N-Fe_(9)Ni_(9)S_(16)/FeS-3@CNTs demonstrates remarkable electrochemical performance,achieving a substantial reversible capacity of up to 682.1mA h g^(−1)for SIBs at 0.1 A g^(−1)and 782.7 mA h g^(−1)for LIBs at 0.5 A g−1,alongside exceptional cycling stability in SIBs,maintaining 78.7%of its capacity after 1500 cycles at 1 A g^(−1)coupling with the ether-based electrolyte.Employing various electrochemical analyses in conjunction with ex-situ characterization techniques and Density Functional Theory(DFT)calculations,the storage mechanisms and phase transition processes are investigated,elucidating the structure-composition-performance relationships.This work paves the way for a new strategy in designing advanced materials with engineered heterostructures and controllable defects for energy conversion and storage devices.展开更多
Developing single-crystalline Ni-rich cathodes is an effective strategy to improve the safety and cycle life of Li-ion batteries(LIBs).However,the easy-to-loss of Li and O in high-temperature lithiation results in uns...Developing single-crystalline Ni-rich cathodes is an effective strategy to improve the safety and cycle life of Li-ion batteries(LIBs).However,the easy-to-loss of Li and O in high-temperature lithiation results in unsatisfactory ordered layered structure and stoichiometry.Herein,we demonstrate the synthesis of highly-ordered and fully-stoichiometric single-crystalline LiNi_(0.83)Co_(0.12)Mn_(0.05)O_(2)(SC-NCM83)cathodes by the regulation of pre-lithiation kinetics.The well-balanced pre-lithiation kinetics have been proved to greatly improve the proportion of layered phase in the intermediate by inhibiting the formation of metastable spinel phase,which promoted the rapid transformation of the intermediate into highly-ordered layered SC-NCM83 in the subsequent lithiation process.After coating a layer of Li_(2)O–B_(2)O_(3),the resultant cathodes deliver superior cycling stability with 90.9%capacity retention at 1C after 300 cycles in pouch-type full batteries.The enhancement mechanism has also been clarified.These findings exhibit fundamental insights into the pre-lithiation kinetics process for guiding the synthesis of high-quality singlecrystalline Ni-rich cathodes.展开更多
Fast-charging and low temperature operation are of vital importance for the further development of lithium-ion batteries(LIBs),which is hindered by the utilization of conventional carbonate-based electrolytes due to t...Fast-charging and low temperature operation are of vital importance for the further development of lithium-ion batteries(LIBs),which is hindered by the utilization of conventional carbonate-based electrolytes due to their slow kinetics,narrow operating temperature and voltage range.Herein,an acetonitrile(AN)-based localized high-concentration electrolyte(LHCE)is proposed to retain liquid state and high ionic conductivity at ultra-low temperatures while possessing high oxidation stability.We originally reveal the excellent thermal shielding effect of non-solvating diluent to prevent the aggregation of Li^(+) solvates as temperature drops,maintaining the merits of fast Li transport and facile desolvation as at room temperature,which bestows the graphite electrode with remarkable low temperature performance(264 mA h g^(-1) at-20 C).Remarkably,an extremely high capacity retention of 97%is achieved for high-voltage high-energy graphite||NCM batteries after 250 cycles at-20 C,and a high capacity of 110 mA h g^(-1)(71%of its room-temperature capacity)is retained at-30°C.The study unveils the key role of the non-solvating diluents and provides instructive guidance in designing electrolytes towards fast-charging and low temperature LIBs.展开更多
As the global electric vehicle market continues to grow,the recycling of Li-ion battery (LIB) becomes more important worldwide and the resynthesis of cathode materials would be the most value-added recycling approach ...As the global electric vehicle market continues to grow,the recycling of Li-ion battery (LIB) becomes more important worldwide and the resynthesis of cathode materials would be the most value-added recycling approach taking into account limited metal resources.Although resynthesized homogenous LiNi_(x)Co_(y)Mn_(z)O_(2)(NCM) from spent LIB leachate shows comparable battery performance to pristine NCM from virgin materials,there is general concern in its cycling performance.Here,we synthesize core–shell(CS) Ni-rich NCM,which consists of Ni-rich NCM as the core and NCM derived from the original or purified leachate of spent LIBs as the shell.Resynthesized CS Ni-rich NCM exhibits improved rate capability resulting from expanded interslab thickness in the NCM structure.CS Ni-rich NCM from purified LIB leachate shows improvement in cycling performance and thermal stability.It specifically delivers a capacity retention of 86.6%at a high temperature after 80 cycles compared to that (75.0%) of pristine CS Ni-rich NCM.These improvements are caused by a relatively high Mg content on the shell and the widespread distribution of Al through the CS structure.CS Ni-rich NCM derived from spent LIB leachate provides a new alternative approach to conventional LIB recycling methods,which would utilize efficiently limited metal resources for the sustainable LIB production.展开更多
The alloy-type material Sb is widely used in the anode materials of lithium-ion batteries(LIBs)due to its high theoretical specific capacity.However,its serious volume expansion problem during alloying/dealloying of L...The alloy-type material Sb is widely used in the anode materials of lithium-ion batteries(LIBs)due to its high theoretical specific capacity.However,its serious volume expansion problem during alloying/dealloying of Li~+limits its practical application.In this work,C-Sb composite was constructed as anode material of LIBs by electrospinning route for the first time,Sb was introduced into the polyacrylonitrile-based hard carbon and coal tar pitch-based soft carbon composite amorphous carbon fiber with a diameter of 300-600 nm,which realized high cycling stability.The C-Sb-2(the mass ratio of polyacrylonitrile to Sb source is 1:2)electrode displayed charge capacities of 1098.5,930.3,841.7,753.5,643.9 and 545.8 mAh·g^(-1)at 0.1,0.2,0.3,0.5,1 and 2 A·g^(-1),respectively.And when the current density returned to 0.1 A·g^(-1),the charge capacity was 939.3 mAh·g^(-1),revealing good stability and reversibility.The introduction of Sb into the amorphous carbon improved its conductivity and addressed the volume expansion issue of high specific capacity Sb during charge/discharge.Ex-situ XRD analysis confirmed the high reversibility of the C-Sb-2 during charging and discharging.Density functional theory(DFT)calculations revealed the gradual enhancement of the interface interaction between Sb_(x)Li_(y) and amorphous carbon(AMC)with increasing lithium content,contributing to the anchoring of alloy nanoparticles on the AMC surface and buffering the volume change of the alloy.Moreover,the gradual lithiation of Sb facilitated the electron transfer from Sb_(x)Li_(y) to AMC.These findings hold promise for designing lithium storage materials with exceptional performance,highlighting the potential of C-Sb composites as anode materials for efficient next-generation lithium storage.展开更多
Two-dimensional(2D)metal-organic frameworks(MOFs)are rapidly emerging as a unique class of mushrooming family of 2D materials offering distinctive features,such as hierarchical porosity,extensive surface area,easily a...Two-dimensional(2D)metal-organic frameworks(MOFs)are rapidly emerging as a unique class of mushrooming family of 2D materials offering distinctive features,such as hierarchical porosity,extensive surface area,easily available active sites,and versatile,adaptable structures.These promising characteristics have positioned them as highly appealing alternatives for a wide range of applications in energy storage technologies,including lithium batteries.Nevertheless,the poor conductivity and limited stability of 2D MOFs have limited their real applications in electrochemical energy storage.These limitations have therefore warranted ongoing research to enhance the performance of 2D MOFs.Given the significance of 2D MOF-based materials as an emerging class of advanced materials,a multitude of strategy has been devised to address these challenges such as synthesizing 2D conductive MOFs and derivatives along with 2D MOF hybridization.One promising approach involves the use of 2D MOF derivatives,including transition metal oxides,which due to their abundant unsatu rated active metal sites and shorter diffusion paths,offer superior electrochemical performance.Additionally,by combining pristine 2D MOFs with other materials,hybrid 2D MOF materials can be created.These hybrids,with their enhanced stability and conductivity,can be directly utilized as active materials in lithium batteries.In the present review,we categorize 2D MOF-based materials into three distinct groups:pristine 2D MOFs,2D MOFderived materials,and 2D MOF hybrid materials.The synthesis methods for each group,along with their specific applications as electrode materials in lithium-ion batteries,are discussed in detail.This comprehensive review provides insights into the potential of 2D MOFs while highlighting the opportunities and challenges that are present in this evolving field.展开更多
To achieve high-energy-density and safe lithium-metal batteries(LMBs),solid-state electrolytes(SSEs)that exhibit fast Li-ion conductivity and good stability against lithium metal are of great importance.This study pre...To achieve high-energy-density and safe lithium-metal batteries(LMBs),solid-state electrolytes(SSEs)that exhibit fast Li-ion conductivity and good stability against lithium metal are of great importance.This study presents a systematic exploration of selenide-based materials as potential SSE candidates.Initially,Li_(8)SeN_(2)and Li_(7)PSe_(6)were selected from 25 ternary selenides based on their ability to form stable interfaces with lithium metal.Subsequently,their favorable electronic insulation and mechanical properties were verified.Furthermore,extensive theoretical investigations were conducted to elucidate the fundamental mechanisms underlying Li-ion migration in Li_(8)SeN_(2),Li_(7)PSe_(6),and derived Li_(6)PSe_(5)X(X=Cl,Br,I).Notably,the highly favorable Li-ion conduction mechanism of vacancy diffusion was identified in Li6PSe5Cl and Li_(7)PSe_(6),which exhibited remarkably low activation energies of 0.21 and 0.23 eV,and conductivity values of 3.85×10^(-2)and 2.47×10^(-2)S cm^(-1)at 300 K,respectively.In contrast,Li-ion migration in Li_(8)SeN_(2)was found to occur via a substitution mechanism with a significant diffusion energy barrier,resulting in a high activation energy and low Li-ion conductivity of 0.54 eV and 3.6×10^(-6)S cm^(-1),respectively.Throughout this study,it was found that the ab initio molecular dynamics and nudged elastic band methods are complementary in revealing the Li-ion conduction mechanisms.Utilizing both methods proved to be efficient,as relying on only one of them would be insufficient.The discoveries made and methodology presented in this work lay a solid foundation and provide valuable insights for future research on SSEs for LMBs.展开更多
Manufacturing process,diffusion co-efficient and areal capacity are the three main criteria for regulating thick electrodes for lithium-ion batteries(LIBs).However,simultaneously regulating these criteria for LIBs is ...Manufacturing process,diffusion co-efficient and areal capacity are the three main criteria for regulating thick electrodes for lithium-ion batteries(LIBs).However,simultaneously regulating these criteria for LIBs is desirable but remains a significant challenge.In this work,niobium pentoxide(Nb_(2)O_(5))anode and lithium iron phosphate(LiFePO_(4))cathode materials were chosen as the model materials and demonstrate that these three parameters can be simultaneously modulated by incorporation of micro-carbon fibers(MCF)and carbon nanotubes(CNT)with both Nb_(2)O_(5) and LFP via vacuum filtration approach.Both as-prepared MNC-20 anode and MLC-20 cathode achieves high reversible areal capacity of≈5.4 m A h cm^(-2)@0.1 C and outstanding Li-ion diffusion coefficients of≈10~(-8)cm~2 s~(-1)in the half-cell configuration.The assembled MNC-20‖MLC-20 full cell LIB delivers maximum energy and power densities of244.04 W h kg^(-1)and 108.86 W kg^(-1),respectively.The excellent electrochemical properties of the asprepared thick electrodes can be attributed to the highly conductive,mechanical compactness and multidimensional mutual effects of the MCF,CNT and active materials that facilitates rapid Li-ion diffusion kinetics.Furthermore,electrochemical impedance spectroscopy(EIS),symmetric cells analysis,and insitu Raman techniques clearly validates the enhanced Li-ion diffusion kinetics in the present architecture.展开更多
Surface modification of graphite anode with electroactive matters has been proven of a more practical strategy in enhancing the performance of Li-ion batteries than exploring alternative novel anode materials.Herein,r...Surface modification of graphite anode with electroactive matters has been proven of a more practical strategy in enhancing the performance of Li-ion batteries than exploring alternative novel anode materials.Herein,rutile TiNbO_(4-x) nanoparticles with a tunnel structure are employed as multifunctional decoration substances in combination with a carbon coating layer to improve the rate and cycle properties of mesocarbon microbeads(MCMBs).As compared to pristine MCMB,the Li^(+)diffusion coefficients of the composite anodes are enhanced due to the synergistic effect of TiNbO_(4-x)@C.Meanwhile,the overcharge and voltage polarization of the composite anodes at high rate are obviously minimized due to the current sharing effect of the high-potential TiNbO_(4-x).Moreover,the amorphous Li_(y)TiNbO_(4-x) converted from TiNbO_(4-x) in the initial lithiation process can deliver pseudocapacitive capacity to the composite anodes from the second cycle.All of these functions of TiNbO_(4-x)@Ccoating layer have directly contributed to the improved rate and cycle performance of the MCMB/TiNbO_(4-x)@C composite anodes.The one containing 12.0 wt%TiNbO_(4-x) exhibits a high reversible specific capacity of 118 m Ah·g^(-1)at 10C(1C=372 m A·g^(-1)),together with a high capacity retention of 90.9%after 300 cycles at 3C,which are all much superior to those of pristine MCMB.展开更多
This review highlights the importance of recovering valuable metals from spent Li-ion battery(LIB)cathodes through the resynthesis of cathode active materials(CAMs).The resynthesis process of CAMs,a promising recyclin...This review highlights the importance of recovering valuable metals from spent Li-ion battery(LIB)cathodes through the resynthesis of cathode active materials(CAMs).The resynthesis process of CAMs,a promising recycling method that directly produces CAM precursors from LIB leachate,is explored.This process encompasses six key steps,including pretreatment,leaching,purification,adjustment of metal concentrations,precursor synthesis,and sintering.The review also investigates the potential introduction of impurity elements during CAM resynthesis and provides tolerance levels for these impurities based on thorough reference analysis.Additionally,it addresses challenges related to the commercialization of the resynthesis process.Notably,this review represents the first comprehensive assessment of CAM resynthesis,including the systematic evaluation of 12 impurity elements(Fe,Li,Al,Cu,C,P,F,Na,Cl,S,Mg,and Zn).Overall,this comprehensive review is poised to support the commercial development of resynthesized CAMs by offering valuable guidelines for managing impurities and streamlining the purification process.展开更多
The electrochromic Li-ion batteries(ELIBs) combine the functions of electrochromism and energy storage,realizing the display of energy-storage levels by visual signals. However, the accompanying interfacial issues inc...The electrochromic Li-ion batteries(ELIBs) combine the functions of electrochromism and energy storage,realizing the display of energy-storage levels by visual signals. However, the accompanying interfacial issues including physical contact and(electro)chemical stability should be taken into account when the conventional liquid/gel electrolytes are replaced with solid-state counterparts. Herein, the in-situ liquid-solid transitional succinonitrile(SCN) plastic glues are constructed between electrodes and poly(ethylene oxide)(PEO) polymer electrolytes, enabling an interface-reinforced solid-state ELIB.Specifically, the liquid SCN precursor can adequately wet electrode/PEO interfaces at high temperature,while it returns back to solid state at room temperature, leading to seamless interfacial contact and smooth ionic transfer without changing the solid state of the device. Moreover, the SCN interlayer suppresses the direct contact of PEO with electrodes containing high-valence metal ions, evoking the improved interfacial stability by inhibiting the oxidation of PEO. Therefore, the resultant solid-state ELIB with configuration of LiMn_(2)O_(4)/SCN-PEO-SCN/WO_(3) delivers an initial discharge capacity of 111 m A h g^(-1) along with a capacity retention of 88.3% after 200 cycles at 30 ℃. Meanwhile, the electrochromic function is integrated into the device by distinguishing its energy-storage levels through distinct color changes. This work proposes a promising solid-state ELIB with greatly reinforced interfacial compatibility by introducing in-situ solidified plastic glues.展开更多
基金supported by the National Key R&D Program of China(No.2022YFE0207400)supported by the Xiaomi Young Talents Programsupported by the Youth Innovation Promotion Association CAS(No.Y201768)。
文摘Na-ion batteries are considered a promising next-generation battery alternative to Li-ion batteries,due to the abundant Na resources and low cost.Most efforts focus on developing new materials to enhance energy density and electrochemical performance to enable it comparable to Li-ion batteries,without considering thermal hazard of Na-ion batteries and comparison with Li-ion batteries.To address this issue,our work comprehensively compares commercial prismatic lithium iron phosphate(LFP) battery,lithium nickel cobalt manganese oxide(NCM523) battery and Na-ion battery of the same size from thermal hazard perspective using Accelerating Rate Calorimeter.The thermal hazard of the three cells is then qualitatively assessed from thermal stability,early warning and thermal runaway severity perspectives by integrating eight characteristic parameters.The Na-ion cell displays comparable thermal stability with LFP while LFP exhibits the lowest thermal runaway hazard and severity.However,the Na-ion cell displays the lowest safety venting temperature and the longest time interval between safety venting and thermal runaway,allowing the generated gas to be released as early as possible and detected in a timely manner,providing sufficient time for early warning.Finally,a database of thermal runaway characteristic temperature for Li-ion and Na-ion cells is collected and processed to delineate four thermal hazard levels for quantitative assessment.Overall,LFP cells exhibit the lowest thermal hazard,followed by the Na-ion cells and NCM523 cells.This work clarifies the thermal hazard discrepancy between the Na-ion cell and prevalent Li-ion cells,providing crucial guidance for development and application of Na-ion cell.
基金supported by the National Natural Science Foundation of China(Nos.22379052,22479062 and 52102252)Taishan Scholars of Shandong Province(No.tsqnz20221143)Independent Cultivation Program of Innovation Team of Ji’nan City(No.202333042).
文摘The unique oxygen stacking sequence of O2-type structures restricts the irreversible transition metal movement into Li vacancies for the delithiated Li-rich layered oxides(LLOs)and maintains outstanding voltage stability.However,the ion-exchange synthesis promotes the Mn-ion valence reduction and aggravates the Jahn-Teller(J-T)distortion alongside disproportionation.Since the main oxidation state of the Mn ions is+4 in the traditional O3-type LLOs,synergistic effects of the O2-type and O3-type structures are expected in the O2/O3 diphasic Li-rich material.Herein,O2/O3 biphasic intergrowth LLOs were rationally designed,and the synergic optimization of the biphasic structure was planned to retard the J-T effect.The O2/O3 intergrowth nature was confirmed,and the percentages of the O2 and O3 phases were 56%and 44%,respectively.Density functional theory calculations demonstrated that the Mn^(2+)(EC)sheath had a remarkably lower energy barrier than the Li^(+)(EC)sheath.This finding suggests that Mn^(2+)ions that are dissolved into the electrolyte accelerate the electrolyte oxidization,so the deposition of the cathode electrolyte interface for pristine O2-LLOs causes a high electrochemical impedance.The designed O2/O3 biphasic LLOs boost the capacity stability and suppress the voltage drop upon repeated Li^(+)de-intercalation.The phase regulation strategy offers great potential for developing low-cost LLOs with enhanced structural stability for advanced Li-ion batteries.
基金supported by the National Natural Science Foundation of China(22479092,22078190)。
文摘In optimizing fast charge capability,mitigating side reaction rate,and unveiling particle cracking tolerance for Li-ion batteries(LIBs),the galvanostatic charge–discharge(GCD)at different charge/discharge rates,the static electrochemical impedance spectroscopy(SEIS)under open circuit voltage(OCV)conditions,and the dynamic EIS(DEIS)under dynamic conditions are widely used to investigate charge transfer reactions in LIBs.In spite of great progresses achieved,it is still an open question how to decouple charge transfer reactions under dynamic conditions,especially under conditions of different charge/discharge rates and state of charges(SOCs).To address the above challenges,this work develops a unified framework to digitize,visualize,and finally decouple charge transfer reactions in LIBs under dynamic conditions.In detail:(i)a set of matrix-based numerical solutions to GCD,SEIS,and DEIS are deduced for LIBs;(ii)an open-source DEIS-Toolbox@LIB to digitize/visualize charge transfer reactions is developed;(iii)EIS under dynamic and OCV conditions are discriminated;and(iv)a dynamic decoupling of charge transfer reactions is achieved with respect to core parameters under dynamic conditions for LIBs.The developed framework serves to digitize/visualize/decouple charge transfer reactions under dynamic conditions,and then to unveil limiting factors of fast charge/discharge and triggering mechanisms of side reactions for batteries.
基金supported by the National Natural Science Foundation of China(U22A20429 and 22308103)Shanghai Pilot Program for Basic Research(22TQ1400100-13)+2 种基金Postdoctoral Fellowship Program of CPSF(GZB20230214)China Postdoctoral Science Foundation(2023M731083)the Fundamental Research Funds for the Central Universities.
文摘Developing cost-effective single-crystalline Ni-rich Co-poor cathodes operating at high-voltage is one of the most important ways to achieve higher energy Li-ion batteries. However, the Li/O loss and Li/Ni mixing under high-temperature lithiation result in electrochemical kinetic hysteresis and structural instability. Herein, we report a highly-ordered single-crystalline LiNi0.85Co0.05Mn0.10O2(NCM85) cathode by doping K+and F-ions. To be specific, the K-ion as a fluxing agent can remarkably decrease the solid-state lithiation temperature by ~30°C, leading to less Li/Ni mixing and oxygen vacancy. Meanwhile, the strong transitional metal(TM)-F bonds are helpful for enhancing de-/lithiation kinetics and limiting the lattice oxygen escape even at 4.5 V high-voltage. Their advantages synergistically endow the single-crystalline NCM85 cathode with a very high reversible capacity of 222.3 mAh g-1. A superior capacity retention of 91.3% is obtained after 500 times at 1 C in pouch-type full cells, and a prediction value of 75.3% is given after cycling for 5000 h. These findings are reckoned to expedite the exploitation and application of high-voltage single-crystalline Ni-rich cathodes for next-generation Li-ion batteries.
基金supported by National Natural Science Foundation of China(Grant No.62403475).
文摘With the widespread adoption of electric vehicles and energy storage systems,predicting the remaining useful life(RUL)of lithium-ion batteries(LIBs)is critical for enhancing system reliability and enabling predictive maintenance.Traditional RUL prediction methods often exhibit reduced accuracy during the nonlinear aging stages of batteries and struggle to accommodate complex degradation processes.This paper introduces a novel adaptive long short-term memory(LSTM)approach that dynamically adjusts observation and prediction horizons to optimize predictive performance across various aging stages.The proposed method employs principal component analysis(PCA)for dimensionality reduction on publicly available NASA and Mendeley battery datasets to extract health indicators(HIs)and applies K-means clustering to segment the battery lifecycle into three aging stages(run-in,linear aging,and nonlinear aging),providing aging-stage-based input features for the model.Experimental results show that,in the NASA dataset,the adaptive LSTM reduces the MAE and RMSE by 0.042 and 0.043,respectively,compared to the CNN,demonstrating its effectiveness in mitigating error accumulation during the nonlinear aging stage.However,in the Mendeley dataset,the average prediction accuracy of the adaptive LSTM is slightly lower than that of the CNN and Transformer.These findings indicate that defining aging-stage-based adaptive observation and prediction horizons for LSTM can effectively enhance its performance in predicting battery RUL across the entire lifecycle.
基金the financial support from the National Natural Science Foundation of China (22472040)the Basic and Applied Basic Research Foundation of Guangdong Province (2023A1515012033)。
文摘The integration of photocatalysis with electrochemical energy storage offers promising solutions for offgrid power supply. Herein, carbon cloth-supported TiO_(2)nanorod arrays are engineered as a model platform to explore photoelectrochemical synergy in integrated photo-rechargeable lithium-ion batteries(PRLiBs). Through operando characterizations and theory calculations, we found that photoexcitation lowers the Li^(+)migration barrier by 0.16 eV through electronic states redistribution near the Fermi level,thereby accelerating Li^(+)transport and enhancing the intercalation process during photo-assisted charging and discharging. Three key principles governing dual operational modes(light-assisted charge/discharge and pure light charging) are established for PRLiBs:(i) the capacity enhancement during photoassisted charging is primarily due to photocatalytic Li^(+)extraction via hole-driven oxidation at the TiO_(2)/electrolyte interface and electric double-layer reconstruction;(ii) the long-standing controversy in solar-to-electricity conversion efficiency(g) is resolved by introducing a polarization-decoupled model to quantify g, distinguishing genuine catalytic contributions from parasitic self-charging effects;and(iii)during light-only charging without external bias, the capacity increase is predominantly driven by the photocatalytic oxidation of the TiO_(2)photoelectrode, a single-electrode process without electron transfer through an external circuit, distinct from conventional dual-electrode charging. This work lays a solid theoretical foundation for understanding the mechanisms of PRLiBs and provides precise guidelines for g calculations, offering valuable insights for the future development of photo-energy storage devices.
基金supported by the Beijing Municipal Natural Science Foundation(L223009)the National Natural Science Foundation of China(22209014,22479012)+1 种基金the Hebei Natural Science Foundation(E2024208084)the Fundamental Research Funds for the Central Universities(2023CX01031)。
文摘Sulfide-based all-solid-state lithium metal batteries(ASSLMBs)have garnered significant attention due to their potential for high energy density and enhanced safety.However,their practical application is hindered by challenges such as uneven lithium(Li)deposition and the growth of Li dendrites.In this contribution,we propose an amorphous fluorinated interphase(AFI),composed of amorphous LiF and lithiated graphite,to regulate the interfacial Li-ion transport kinetics through in-situ interface chemistry.Amorphous LiF,which exhibits a significantly enhanced Li-ion diffusion compared to its crystalline counterpart,works synergistically with lithiated graphite to promote both short-range and long-range Li-ion transport kinetics at the Li/electrolyte interface.As a result,the Li anode with AFI demonstrates a remarkably enhanced critical current density of 1.6 mA cm^(−2)and an extended cycle life exceeding 1100 h.The Li||LiNi_(0.6)Co_(0.2)Mn_(0.2)O_(2)full cell also achieves a high discharge capacity of 125.7 mA h g^(−1)and retains 71.2%of its initial capacity after 200 cycles.This work provides valuable insights into the rational design of artificial anodic interphase to regulate interfacial Li-ion transport kinetics in ASSLMBs.
基金supported by the National Natural Science Foundation of China(22075170)employed resources from the BL11B station of the Shanghai Synchrotron Radiation Facility(SSRF,under contract number:2023-SSRF-PT-502681)。
文摘Increasing the charging cut-off voltage can significantly enhance the energy density of LiCoO_(2).However,the continuous deterioration of interface structure and transport kinetics under high voltage poses challenges to electrochemical stability.This work proposes to in-situ construct a uniform element gradient modification structure on the surface and subsurface of LiCoO_(2).The modification structure contains an Sb_(2)O_(3)&SbF_(x)composite coating layer and an Sb-F doped spinel-like transition layer,simultaneously.The modified sample maintains an initial discharge specific capacity of 221.2 mA h g^(-1)and a capacity retention of 86%after 200 cycles at 3–4.6 V and 0.5 C.Moreover,it has a discharge specific capacity of163.3 mA h g^(-1)at a high rate of 5 C.Meanwhile,combining highly electronegative Sb^(3+)&F^(-)that widen the Li^(+)transport channel with the amorphous coating of F^(-)doped Sb_(2)O_(3)with higher conductivity improves the interface transport kinetics.This breaks the stereotypical view in traditional concepts that fluorinated coatings or inert metal oxide coatings inhibit Li^(+)transport.Moreover,the inert composite coating combined with Sb–O–F with high bond energy stabilizes the surface structure.A series of characterizations confirm that the joint improvement of interface structure stability and transport kinetics significantly enhances the electrochemical performance of LiCoO_(2).
基金supported by the Basic Science Research Program through the National Research Foundation of Korea(NRF)funded by the Ministry of Science and ICT(RS-2023-00254424)by the ITRC(Information Technology Research Center)support program(IITP-2024-RS-2024-00437494)supervised by the IITP(Institute for Information&Communications Technology Planning&Evaluation)funded by the MSIT(Ministry of Science and ICT),Korea。
文摘It is of great importance to explore sustainable and eco-friendly recycling strategies for spent Li-ion batteries(LIBs).As such,the closed-loop resynthesis of LiNi_(x)CoyMn_(z)O_(2)(NCM)becomes recently popular as exemplified by the commercialization of low-and mid-Ni content NCM(33%-60%).However,there has been suspicion as to the successful deployment of Ni-rich NCM resynthesis process.Therefore,we systematically increase the Ni content of NCM from 60%to 90%from the industrial leachate of spent LIBs containing various metallic and nonmetallic impurities.The utilization rate of the leachate decreases from 71.8 mol%for NCM622 to 18.0 mol%for NCM955 as the Ni content in the NCM composition increases with the Co recycling rate being 100%in all resynthesized NCM(RNCM).The physicochemical and electrochemical properties of RNCM are systematically compared with its pristine NCM counterparts.As a result,various physicochemical properties of RNCM including impurity content,crystallographic information,morphology,particle size,porosity,specific surface area,elemental distribution,residual lithium compounds,and thermal stability are correlated with its electrochemical properties.It is found out that Al is the most critical impurity that determines the physicochemical and electrochemical properties of RNCM.It is noteworthy that RNCM955 prepared from spent LIBs without any purification step surpasses NCM955 in terms of rate and cycle performance.Further,this resynthesis approach toward Nirich NCM could meet the forthcoming 2031 EU's legislative target on the mandatory minimum recycling usage of valuable metals from spent LIBs.The anode active material was resynthesized using industrial leachate as the maximum.The amount of leachate used and the amount of impurities were proportional.
基金supported by the program of National Research Foundation of Korea(NRF)funded by the Ministry of Science,ICT and Future planning(grant number 2022R1A4A1034312,2023R1A2C1007413)by the Commercialization Promotion Agency for R&D Outcomes(COMPA)grant funded by the Korean Government(Ministery of Science and ICT)(RS-2023-00304764)。
文摘Tailoring 1D nanotubes with refined interfacial interactions and optimized adsorption sites presents a highly promising yet challenging strategy for advancing Na/Li-ion batteries(SIBs/LIBs).Herein,the intertwined yardlong bean-like Fe_(9)Ni_(9)S_(16)/FeS heterostructures with sulfur vacancies encapsulated in N-doped carbon nanotubes(3 N-Fe_(9)Ni_(9)S_(16)/FeS-3@CNTs)are controllably synthesized through Fe/Ni-catalyzed pyrolysis of dicyandiamide followed by sulfidation strategies.1D nanotubes with robust outer walls and internal cavity structures shorten the diffusion paths of ions/electrons and buffer volume expansion and aggregation of active materials.The Fe_(9)Ni_(9)S_(16)/FeS heterostructure provides a powerful driving force for charge transfer by forming built-in electric fields,optimizing ion adsorption,while the Fe_(9)Ni_(9)S_(16)features a wider interlayer spacing that allows for frequent Na+/Li+insertion and extraction,thereby enhancing the reaction kinetics within the electrode.Driven by these synergistic factors,the 3 N-Fe_(9)Ni_(9)S_(16)/FeS-3@CNTs demonstrates remarkable electrochemical performance,achieving a substantial reversible capacity of up to 682.1mA h g^(−1)for SIBs at 0.1 A g^(−1)and 782.7 mA h g^(−1)for LIBs at 0.5 A g−1,alongside exceptional cycling stability in SIBs,maintaining 78.7%of its capacity after 1500 cycles at 1 A g^(−1)coupling with the ether-based electrolyte.Employing various electrochemical analyses in conjunction with ex-situ characterization techniques and Density Functional Theory(DFT)calculations,the storage mechanisms and phase transition processes are investigated,elucidating the structure-composition-performance relationships.This work paves the way for a new strategy in designing advanced materials with engineered heterostructures and controllable defects for energy conversion and storage devices.
基金supported by the National Natural Science Foundation of China(21975074,91834301)the Innovation Program of Shanghai Municipal Education Commissionthe Fundamental Research Funds for the Central Universities.
文摘Developing single-crystalline Ni-rich cathodes is an effective strategy to improve the safety and cycle life of Li-ion batteries(LIBs).However,the easy-to-loss of Li and O in high-temperature lithiation results in unsatisfactory ordered layered structure and stoichiometry.Herein,we demonstrate the synthesis of highly-ordered and fully-stoichiometric single-crystalline LiNi_(0.83)Co_(0.12)Mn_(0.05)O_(2)(SC-NCM83)cathodes by the regulation of pre-lithiation kinetics.The well-balanced pre-lithiation kinetics have been proved to greatly improve the proportion of layered phase in the intermediate by inhibiting the formation of metastable spinel phase,which promoted the rapid transformation of the intermediate into highly-ordered layered SC-NCM83 in the subsequent lithiation process.After coating a layer of Li_(2)O–B_(2)O_(3),the resultant cathodes deliver superior cycling stability with 90.9%capacity retention at 1C after 300 cycles in pouch-type full batteries.The enhancement mechanism has also been clarified.These findings exhibit fundamental insights into the pre-lithiation kinetics process for guiding the synthesis of high-quality singlecrystalline Ni-rich cathodes.
基金supported by the National Natural Science Foundation of China (No.92372123)the Natural Science Foundation of Guangdong Province (No.2022B1515020005)the Department of Science and Technology of Guangdong Province (No.2020B0101030005)
文摘Fast-charging and low temperature operation are of vital importance for the further development of lithium-ion batteries(LIBs),which is hindered by the utilization of conventional carbonate-based electrolytes due to their slow kinetics,narrow operating temperature and voltage range.Herein,an acetonitrile(AN)-based localized high-concentration electrolyte(LHCE)is proposed to retain liquid state and high ionic conductivity at ultra-low temperatures while possessing high oxidation stability.We originally reveal the excellent thermal shielding effect of non-solvating diluent to prevent the aggregation of Li^(+) solvates as temperature drops,maintaining the merits of fast Li transport and facile desolvation as at room temperature,which bestows the graphite electrode with remarkable low temperature performance(264 mA h g^(-1) at-20 C).Remarkably,an extremely high capacity retention of 97%is achieved for high-voltage high-energy graphite||NCM batteries after 250 cycles at-20 C,and a high capacity of 110 mA h g^(-1)(71%of its room-temperature capacity)is retained at-30°C.The study unveils the key role of the non-solvating diluents and provides instructive guidance in designing electrolytes towards fast-charging and low temperature LIBs.
基金supported by Basic Science Research Program through the National Research Foundation of Korea (NRF) funded by the Ministry of Science and ICT (2023R1A2C100571511,RS-2023-00254424)the Ministry of Education(2020R1A6A1A03038540)。
文摘As the global electric vehicle market continues to grow,the recycling of Li-ion battery (LIB) becomes more important worldwide and the resynthesis of cathode materials would be the most value-added recycling approach taking into account limited metal resources.Although resynthesized homogenous LiNi_(x)Co_(y)Mn_(z)O_(2)(NCM) from spent LIB leachate shows comparable battery performance to pristine NCM from virgin materials,there is general concern in its cycling performance.Here,we synthesize core–shell(CS) Ni-rich NCM,which consists of Ni-rich NCM as the core and NCM derived from the original or purified leachate of spent LIBs as the shell.Resynthesized CS Ni-rich NCM exhibits improved rate capability resulting from expanded interslab thickness in the NCM structure.CS Ni-rich NCM from purified LIB leachate shows improvement in cycling performance and thermal stability.It specifically delivers a capacity retention of 86.6%at a high temperature after 80 cycles compared to that (75.0%) of pristine CS Ni-rich NCM.These improvements are caused by a relatively high Mg content on the shell and the widespread distribution of Al through the CS structure.CS Ni-rich NCM derived from spent LIB leachate provides a new alternative approach to conventional LIB recycling methods,which would utilize efficiently limited metal resources for the sustainable LIB production.
基金financially supported by the National Natural Science Foundation of China(No.U1960107)the Natural Science Foundation of Hebei Province(No.E2022501014)+2 种基金the Science and Technology Research Youth Fund Project of Higher Education Institutions of Hebei Province(No.QN2022196)the Fundamental Research Funds for the Central Universities(No.N2123001)the Natural Science Foundation of Hebei Province of China(No.B2020501003)。
文摘The alloy-type material Sb is widely used in the anode materials of lithium-ion batteries(LIBs)due to its high theoretical specific capacity.However,its serious volume expansion problem during alloying/dealloying of Li~+limits its practical application.In this work,C-Sb composite was constructed as anode material of LIBs by electrospinning route for the first time,Sb was introduced into the polyacrylonitrile-based hard carbon and coal tar pitch-based soft carbon composite amorphous carbon fiber with a diameter of 300-600 nm,which realized high cycling stability.The C-Sb-2(the mass ratio of polyacrylonitrile to Sb source is 1:2)electrode displayed charge capacities of 1098.5,930.3,841.7,753.5,643.9 and 545.8 mAh·g^(-1)at 0.1,0.2,0.3,0.5,1 and 2 A·g^(-1),respectively.And when the current density returned to 0.1 A·g^(-1),the charge capacity was 939.3 mAh·g^(-1),revealing good stability and reversibility.The introduction of Sb into the amorphous carbon improved its conductivity and addressed the volume expansion issue of high specific capacity Sb during charge/discharge.Ex-situ XRD analysis confirmed the high reversibility of the C-Sb-2 during charging and discharging.Density functional theory(DFT)calculations revealed the gradual enhancement of the interface interaction between Sb_(x)Li_(y) and amorphous carbon(AMC)with increasing lithium content,contributing to the anchoring of alloy nanoparticles on the AMC surface and buffering the volume change of the alloy.Moreover,the gradual lithiation of Sb facilitated the electron transfer from Sb_(x)Li_(y) to AMC.These findings hold promise for designing lithium storage materials with exceptional performance,highlighting the potential of C-Sb composites as anode materials for efficient next-generation lithium storage.
基金based upon research funded by the Iran National Science Foundation. (INSF)under project No.4022382 and 4025075。
文摘Two-dimensional(2D)metal-organic frameworks(MOFs)are rapidly emerging as a unique class of mushrooming family of 2D materials offering distinctive features,such as hierarchical porosity,extensive surface area,easily available active sites,and versatile,adaptable structures.These promising characteristics have positioned them as highly appealing alternatives for a wide range of applications in energy storage technologies,including lithium batteries.Nevertheless,the poor conductivity and limited stability of 2D MOFs have limited their real applications in electrochemical energy storage.These limitations have therefore warranted ongoing research to enhance the performance of 2D MOFs.Given the significance of 2D MOF-based materials as an emerging class of advanced materials,a multitude of strategy has been devised to address these challenges such as synthesizing 2D conductive MOFs and derivatives along with 2D MOF hybridization.One promising approach involves the use of 2D MOF derivatives,including transition metal oxides,which due to their abundant unsatu rated active metal sites and shorter diffusion paths,offer superior electrochemical performance.Additionally,by combining pristine 2D MOFs with other materials,hybrid 2D MOF materials can be created.These hybrids,with their enhanced stability and conductivity,can be directly utilized as active materials in lithium batteries.In the present review,we categorize 2D MOF-based materials into three distinct groups:pristine 2D MOFs,2D MOFderived materials,and 2D MOF hybrid materials.The synthesis methods for each group,along with their specific applications as electrode materials in lithium-ion batteries,are discussed in detail.This comprehensive review provides insights into the potential of 2D MOFs while highlighting the opportunities and challenges that are present in this evolving field.
基金financially supported by the National Natural Science Foundation of China(Grant No.22273096)the Fundamental Research Funds for Central Universities(20826041G4185)
文摘To achieve high-energy-density and safe lithium-metal batteries(LMBs),solid-state electrolytes(SSEs)that exhibit fast Li-ion conductivity and good stability against lithium metal are of great importance.This study presents a systematic exploration of selenide-based materials as potential SSE candidates.Initially,Li_(8)SeN_(2)and Li_(7)PSe_(6)were selected from 25 ternary selenides based on their ability to form stable interfaces with lithium metal.Subsequently,their favorable electronic insulation and mechanical properties were verified.Furthermore,extensive theoretical investigations were conducted to elucidate the fundamental mechanisms underlying Li-ion migration in Li_(8)SeN_(2),Li_(7)PSe_(6),and derived Li_(6)PSe_(5)X(X=Cl,Br,I).Notably,the highly favorable Li-ion conduction mechanism of vacancy diffusion was identified in Li6PSe5Cl and Li_(7)PSe_(6),which exhibited remarkably low activation energies of 0.21 and 0.23 eV,and conductivity values of 3.85×10^(-2)and 2.47×10^(-2)S cm^(-1)at 300 K,respectively.In contrast,Li-ion migration in Li_(8)SeN_(2)was found to occur via a substitution mechanism with a significant diffusion energy barrier,resulting in a high activation energy and low Li-ion conductivity of 0.54 eV and 3.6×10^(-6)S cm^(-1),respectively.Throughout this study,it was found that the ab initio molecular dynamics and nudged elastic band methods are complementary in revealing the Li-ion conduction mechanisms.Utilizing both methods proved to be efficient,as relying on only one of them would be insufficient.The discoveries made and methodology presented in this work lay a solid foundation and provide valuable insights for future research on SSEs for LMBs.
基金supported by the Science and Technology Innovation Program of Hunan Province(2022WZ1012)the Hunan Joint International Laboratory of Advanced Materials and Technology for Clean Energy(2020CB1007)the Natural Science Foundation of Guangzhou(202201020147)。
文摘Manufacturing process,diffusion co-efficient and areal capacity are the three main criteria for regulating thick electrodes for lithium-ion batteries(LIBs).However,simultaneously regulating these criteria for LIBs is desirable but remains a significant challenge.In this work,niobium pentoxide(Nb_(2)O_(5))anode and lithium iron phosphate(LiFePO_(4))cathode materials were chosen as the model materials and demonstrate that these three parameters can be simultaneously modulated by incorporation of micro-carbon fibers(MCF)and carbon nanotubes(CNT)with both Nb_(2)O_(5) and LFP via vacuum filtration approach.Both as-prepared MNC-20 anode and MLC-20 cathode achieves high reversible areal capacity of≈5.4 m A h cm^(-2)@0.1 C and outstanding Li-ion diffusion coefficients of≈10~(-8)cm~2 s~(-1)in the half-cell configuration.The assembled MNC-20‖MLC-20 full cell LIB delivers maximum energy and power densities of244.04 W h kg^(-1)and 108.86 W kg^(-1),respectively.The excellent electrochemical properties of the asprepared thick electrodes can be attributed to the highly conductive,mechanical compactness and multidimensional mutual effects of the MCF,CNT and active materials that facilitates rapid Li-ion diffusion kinetics.Furthermore,electrochemical impedance spectroscopy(EIS),symmetric cells analysis,and insitu Raman techniques clearly validates the enhanced Li-ion diffusion kinetics in the present architecture.
基金supported by the Natural Science Foundation Project of Fujian Province(Nos.2020J01287 and 2020H0024)。
文摘Surface modification of graphite anode with electroactive matters has been proven of a more practical strategy in enhancing the performance of Li-ion batteries than exploring alternative novel anode materials.Herein,rutile TiNbO_(4-x) nanoparticles with a tunnel structure are employed as multifunctional decoration substances in combination with a carbon coating layer to improve the rate and cycle properties of mesocarbon microbeads(MCMBs).As compared to pristine MCMB,the Li^(+)diffusion coefficients of the composite anodes are enhanced due to the synergistic effect of TiNbO_(4-x)@C.Meanwhile,the overcharge and voltage polarization of the composite anodes at high rate are obviously minimized due to the current sharing effect of the high-potential TiNbO_(4-x).Moreover,the amorphous Li_(y)TiNbO_(4-x) converted from TiNbO_(4-x) in the initial lithiation process can deliver pseudocapacitive capacity to the composite anodes from the second cycle.All of these functions of TiNbO_(4-x)@Ccoating layer have directly contributed to the improved rate and cycle performance of the MCMB/TiNbO_(4-x)@C composite anodes.The one containing 12.0 wt%TiNbO_(4-x) exhibits a high reversible specific capacity of 118 m Ah·g^(-1)at 10C(1C=372 m A·g^(-1)),together with a high capacity retention of 90.9%after 300 cycles at 3C,which are all much superior to those of pristine MCMB.
基金supported by the National Research Foundation of Korea(NRF)grant funded by the Korea government(Ministry of Science and ICT(RS-2023-00254424)Ministry of Education(2020R1A6A1A03038540))。
文摘This review highlights the importance of recovering valuable metals from spent Li-ion battery(LIB)cathodes through the resynthesis of cathode active materials(CAMs).The resynthesis process of CAMs,a promising recycling method that directly produces CAM precursors from LIB leachate,is explored.This process encompasses six key steps,including pretreatment,leaching,purification,adjustment of metal concentrations,precursor synthesis,and sintering.The review also investigates the potential introduction of impurity elements during CAM resynthesis and provides tolerance levels for these impurities based on thorough reference analysis.Additionally,it addresses challenges related to the commercialization of the resynthesis process.Notably,this review represents the first comprehensive assessment of CAM resynthesis,including the systematic evaluation of 12 impurity elements(Fe,Li,Al,Cu,C,P,F,Na,Cl,S,Mg,and Zn).Overall,this comprehensive review is poised to support the commercial development of resynthesized CAMs by offering valuable guidelines for managing impurities and streamlining the purification process.
基金National Natural Science Foundation of China (Grant Nos. 22379077 and 22005163)。
文摘The electrochromic Li-ion batteries(ELIBs) combine the functions of electrochromism and energy storage,realizing the display of energy-storage levels by visual signals. However, the accompanying interfacial issues including physical contact and(electro)chemical stability should be taken into account when the conventional liquid/gel electrolytes are replaced with solid-state counterparts. Herein, the in-situ liquid-solid transitional succinonitrile(SCN) plastic glues are constructed between electrodes and poly(ethylene oxide)(PEO) polymer electrolytes, enabling an interface-reinforced solid-state ELIB.Specifically, the liquid SCN precursor can adequately wet electrode/PEO interfaces at high temperature,while it returns back to solid state at room temperature, leading to seamless interfacial contact and smooth ionic transfer without changing the solid state of the device. Moreover, the SCN interlayer suppresses the direct contact of PEO with electrodes containing high-valence metal ions, evoking the improved interfacial stability by inhibiting the oxidation of PEO. Therefore, the resultant solid-state ELIB with configuration of LiMn_(2)O_(4)/SCN-PEO-SCN/WO_(3) delivers an initial discharge capacity of 111 m A h g^(-1) along with a capacity retention of 88.3% after 200 cycles at 30 ℃. Meanwhile, the electrochromic function is integrated into the device by distinguishing its energy-storage levels through distinct color changes. This work proposes a promising solid-state ELIB with greatly reinforced interfacial compatibility by introducing in-situ solidified plastic glues.
